Freestanding, binder-free supercapacitor electrodes based on high-purity polyaniline (PANT) nanofibers were fabricated via a single step electrospinning process. The successful electrospinning of nanofibers with an unprecedentedly high composition of PANI (93 wt %) was made possible due to blending ultrahigh molecular weight poly(ethylene oxide) (PEO) with PANI in solution to impart adequate chain entanglements, a critical requirement for electrospinning. To further enhance the conductivity and stability of the electrodes, a small concentration of carbon nanotubes (CNTs) was added to the PANI/PEO solution prior to electrospinning to generate PANI/CNT/PEO nanofibers (12 wt % CNTs). Scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) porosimetry were conducted to characterize the external morphology of the nanofibers. The electrospun nanofibers were further probed by transmission electron microscopy (TEM), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FT-IR). The electroactivity of the freestanding RANI and PANI/CNT nanofiber electrodes was examined using cyclic voltammetry, galvanostatic charge discharge, and electrochemical impedance spectroscopy. Competitive specific capacitances of 308 and 385 F g(-1) were achieved for PANI and PANI-CNT based electrodes, respectively, at a current density of 0.5 A g(-1). Moreover, specific capacitance retentions of 70 and 81.4% were observed for PANI and PANI-CNT based electrodes, respectively, after 1000 cycles. The promising electrochemical performance of the fabricated electrodes; we believe, stems from the porous 3-D electrode structure characteristic of the nonwoven interconnected nanostructures. The interconnected nanofiber network facilitates efficient electron conduction while the inter- and intrafiber porosity enable excellent electrolyte penetration within the polymer matrix, allowing fast ion transport to the active sites.